Composition of and method of using nanoscale materials in hydrogen storage applications

This application is based on and claims priority to U.S. Provisional Patent Application No. 61/046,790, filed on Apr. 21, 2008, and entitled “COMPOSITION OF AND METHOD OF USING NANOSCALE MATERIALS IN HYDROGEN STORAGE APPLICATIONS,” the entire contents of which is hereby expressly incorporated by reference.

1. Field

The disclosure generally relates to electrodes and applications utilizing electrodes, such as batteries and fuel storage devices.

2. Description of the Related Art

Solid state storage of hydrogen via absorption into a chemical or metal hydride matrix is widely viewed as a promising alternative to storage of hydrogen as a liquid or under high compression as a gas. The principle is presently used in rechargeable batteries such as nickel-metal hydride (NiMH) batteries, in which hydrogen is reversibly absorbed into the anode electrode during battery cycling. By increasing the rate of the hydrogen absorption-desorption reaction, the rate capability of the battery can be improved. Over the last 30 years, considerable effort by researchers around the world has been directed towards improvement of NiMH electrodes and batteries to extend their commercial applications, as these batteries present a number of positive characteristics, such as previous market-proven durability, relatively low cost, no toxic materials (such as cadmium), safety, and good specific energy (˜280 Wh/l) and energy density (˜80 Wh/kg).

In a NiMH battery anode, the active materials are typically AB₅ rare-earth alloys containing predommantly La, Ce, Pr, and Nd (mischmetal), Al or Ni. Considerable efforts have been focused on the development of an improved composition by the incorporation of other elements into the alloy. In an effort to increase capacity and service life, Matsumara et al. have added group VIIB, group VIII, and group IB elements into the alloy through the use of acidic treatments. Additionally, Fetcenko et al. have focused on hydrogen storage alloys containing V, Ti, Zr, Ni, Zr, Co, Mn, Fe, and Sn to improve energy density, cycle life, and low temperature performance. Ovshinsky and Young added palladium into the alloy for improved rate capability, and Jacobus et al. added Ni, Pd, Pt, Ir or Rh via electroless plating upon the surface of the base alloy to improve low temperature operational performance. More recently, Yuko et al. focused on the addition of a layer of fine Ni particles on one face of a hydrogen absorbing alloy to improve current collection and rate capability. The layer was formed by blade casting a paste of Ni particles in a copolymer to an iron sheath which is in contact with the outer anode can of the battery. Likewise, Nakayama et al. provided a layer of fine Ni atop a carbon layer in proximity to the current collector face.

While the prior art hydrogen storage alloys and negative electrode modified compositions improve at least one battery performance characteristic, most were focused on the complex integration of new metals alloyed into the base matrix and therefore additional chemical preparations steps were necessary to form new base alloys. This can provide significant cost increases that inhibit commercialization, especially if the integration requires more processing steps or if the material to be integrated is a precious metal. Furthermore, by coating only the surface of the anode electrode with fine particles, many of the potential benefits are lost as Ni, in and of itself, is an active material in the kinetics of hydrogen absorption and de-sorption. Additionally, the prior art does not describe the role of metal oxide additives in the improvement of NiMH anode electrode kinetics. For example, Yusa discloses that the method of preparation requires steps to prevent the formation of any oxide on nanoparticles.

Described herein are compositions and uses of nanoscale additives in electrode and/or hydrogen storage applications. Compositions are provided that comprise or that consist of metal hydrides together with a certain percentage of nano-sized reactive metal particles, preferably nickel, manganese, aluminum, cobalt, copper, tin, palladium, silver, gold, lanthanum, and/or combinations or alloys thereof. The addition of nano-metals enhances the hydrogen charging characteristics of the battery. These compositions have use, for example, in an electrode in a Nickel-Metal-Hydride battery as well as a hydrogen storage material in a fuel cell or hydrogen combustion engine.

In at least one embodiment, a composition is provided comprising a metal hydride and a plurality of nano-sized particles of reactive metal particles. The composition can be suitable for application as an electrode in a nickel-metal hydride battery or hydrogen storage material in a fuel storage system.

In various embodiments, the nano-sized metal particles can comprise between 0.1 wt % and 30 wt % of the overall composition, such as between 1 wt % and 5 wt % or between 5 wt % and 10 wt % of the overall composition. The nano-sized metal particles can be selected from groups IIA, IB, and IIIB-VIIIB of the periodic table. For instance, the nano-sized metal particles can comprise one or more of nickel, manganese, aluminum, cobalt, copper, tin, palladium, silver, gold, lanthanum, and/or alloys thereof. The metal hydride can comprise a multi-component alloy with a nickel and/or nickel alloy enriched surface coating.

In at least one embodiment, an electrode is provided comprising any of the compositions described above. In at least one embodiment, a hydrogen storage device is provided comprising any of the compositions described above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a TEM microscope image of a metal particle with an oxide shell.

FIG. 2 illustrates discharge curves at C-Rate for NiMH coin cells using various anode nanoparticle additives.

FIG. 3 illustrates percentage of capacity as a function of hours charged after formation.

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